Trustee



Patented Apr. 12, 1927.

UNITE STAT :ii

CHARLES O. TERWILLIGER, OF BEACON, NEW YORK, ASSIGNOR 'IO FRITZ V. BRIESEN,

TRUSTEE, OF NEW YORK, N. Y.

RESILIAND PROCESS OF MAKING THE SAME.

No-Drawi'ng. Applicationifiled July 5, 1923, Se rialNo. 649,720. Renewed February 7, 1927.

invention relates to certain new resins which contain in combination the following. substances: aphenolic body, a ketonic body. and a formaldehyde body. Generally speaking, any one specific group of these substances appears to enter into three, or at least three, specific relations as shown by the fact that in one relation the product IS fusible and soluble, in another fusible and insoluble, and in a third infusible and insoluble.

My invention relates, furthermore, to the process by which these resins may be produced, and I desire it to be understood that I claim such process whether or not it IS modified so as to produce a different product, and that I claim my new resins whether or not they are produced by the .said process.

For producing my new resins, I place in reactive relation a member of each of the following groups of substances:

1. A phenolic body, for instance any one of the following or a mixture of two or more thereof:

The phenolic bodies found in coal-taro l and distillable therefrom between approxlmately 184 C. and 224 Q, or produced synthetically, such as phenol, the cresols, the xylenols and the pyro-cresols; all mono-, d 30 and tri-hydroxy phenols,.whether found in nature or produced synthetically; the phenol alcohols; as very readily available for manufacturing purposes on a large scale I may use the entire cut of the distillation of coal-' tar oil betwen the limits above given or a proportion of such cut,or so-called crude coal-tar oils which contain various proportions of phenolic bodies, most of the phenol having first been removed,or so-called middle oil produced by the distillation of coal-tar oil between 165 C. and 230 (3., and the crude naphthalene then removed. I have had excellent results when using ortho-cresol or para -cresol or a mixture of them without any essential modification of my process.

2. Para-formaldehyde, or a water solution of formaldehyde, the latter not so effectively because of its water content. Hexa-methylene tetramine which, upon heating, breaks up into ammonia and formaldehyde, may be used in place of either of these two substances. In my claims I group these three substances under the designation formaldehyde body. As an equivalent I may use furfuraldehyde.

of ketones, prefi total Weight of the substances of groups 1 and 3, although this proportion may be varied within certain limits that may be readily ascertained by simple experiment in accordance with the particular nature of the other ingredients. In order readily to bring about a combination of these substances, I introduceinto the mixture thereof an alkaline catalyst such as an alkaline hydroxid or an alkaline carbonate, preferably sodium or potassium hydroxid. The'proportion of catalyst is preferably from one-fiftieth to one-tenth of the proportion of its molecular weight to the total molecular. weight of the three inv gredients to be combined; the proper amount can readily be determined by .adding the catalyst to the mixture slowly until the re-- action starts and continues satisfactorily. If no catalyst be used the mixture will react if submitted to sufficient pressure and heat, and heat may at times be used profitably if a catalyst is used. An acid catalyst may be used, but I prefer not to use it, as it does not give the best results, and must be removed from the resin as it would attack the metal of the mold.

If the ingredients are allowed. to react, they will first form new resins which are soluble and fusible; upon further heating such resins will be converted into resins which are insoluble and fusible, which resins in turn will, upon further heating, be converted into resins which are insoluble and mo infusible. The insoluble and infusible resins may be used in the manufacture of articles of many kinds, as they have high tensile strength andhi-gh di-electric properties. In order to manufacture such articles by molding,the soluble and fusible resin, or the insoluble and fusible resin, is placed into a mold and therein treated with heat to convert it into the insoluble and infusible resin,

pressure being applied at the same time. A

filler, such as asbestos or sawdust, may be admixed to the resins before it isplaced in .the mold. The soluble and -f'usible resin may be employed in proper solution as a varnish, which" after application. is heated for conversion into the insoluble and 'infusible resin. The following example will illustrate the rocess by which I produce m'y resins:

Oil distilled from so-called coal-tar oil between 184 C. and 224 C. is preferably first treated, by redistillation or otherwise,

to remove tarry matter or free carbon. One hundred .(100) parts of such oil are placed with thirty parts of a ketone, preferably. acetone, and fifty (50) parts of paraformaldehyde into a suitable vesselprovided with heatingand cooling means, an agitator and a reflux condenser. To the'mixture are added three (3) parts of an alkaline hydroxid, such as sodium or potassium hydroxid, dissolved in as little water as possible, or without water. The contents are agitated for a short time and, if necessary, heat is applied to start the reaction and thereafter, from time to time, to accelerate the reactionif necessary; if the reaction pro- 'ceeds too violently the vessel should be cooled less if necessary, to prevent conversion of the resin into the insoluble and fusible form.

The resin thus produced may be mixed with a suitable solvent, such as alcohol, benzol or acetone and used as a varnish. The solution is applied to thearticle to be varnished, and such article is thepeslowly baked, beginning with normal room mperat'ure, to about 150 C. over a period of approximately five hours or until the resin has been converted into the insoluble and infusible resin.

The resin thus produced may, furthermore, be used for making molded articles. If the article desired is to be translucent, such as a pipe bit, no filler is added and the resin is, further heated until it becomes hard when cooled, and, while it is still in the soluble and fusible form, or'until it has become I I converted (as it will upon longer heating) into the insoluble and fusible resin. The hard resin is then ground to desired fineness, laced into a mold and subjected to heat a out 150 C.) until the resin has been converted into the insoluble and infusible state, suitable pressure being'applied to comact the material.

If the article desired is to contam a filler (sawdust, asbestos, etc.), such filler may be V added tothe soluble and fusible resin while it is still in its liquid state, or may be mixed with the ground hard resin, either the soluble and fusible, or the insoluble and fusible, and the mixture then treated in a mold as herein-above'described. I have found equal weights of resin and sawdust suitable for admixture, but it isobvious that the proportion of filler to resin may vary widely. Suitable coloring-matter may be added to the mixture or to the filler.

No ingredients other than those hereinabove referred to are necessary to produce the molded article, and especially no accelerator, or retarder, or wax.

Instead of. a single ketone, I find it profit- I able to use a mixture of ketones such as may I be contained in what is known commercially as 1i ht oras heavy acetone oils obtained as bgy-products in the distillation of acetone. The acetone oils give as good re sults, commercially, as acetone, and are very much lower in price.

By substituting seventy-five (75) parts of the oils for the hundred parts specified in the above example, and by substitutingforty-five (45) parts of the acetone for the'thirty (30) parts specified in the above example, Iobtain resins similar in behavior, but different in composition, from those obtained by following such example.

-,For the oil above referred to. I may sub stitute in the above example and modification thereof any of the other substances of group 1, (for instance the ortho-cresol and v para-cresol mixture) without any change in the remaining ingredients and proportions thereof.

As the ingredients do not, in their entirety, enter-into reaction, some portion of each ingredient will be left uncombined in the finished resin, and their presence can be detected b the ordinary means of chemical analysis. y resins, therefore, may be identified by reacting to the tests for the ingredients which were used in preparing the same. I

While I do not .know of any combination of materials selected from these three groups hereinabove specified, which, under proper conditions, will not produce one of my new resins, if such combination should be found I do not include it in my process claims.

I claim: 1. A resin which contains in combination a phenolic body, a ketone and a formaldehyde body, and which has been produced b permitting such substances to react simu taneously.

2. A resin. which contains in combination a phenolic body, acetone and a formaldehyde body, and which has been produced by permitting such substances to react simultaneously;

3. A resin which contains in combination a phenolic body, acetone oil and a formaldehyde body, and which has been produced by permitting such substances to react simultaneously. I

4. A resin which contains in combination a phenolic body, acetone oil and para-formaldehyde, and which has been produced b permitting such substances to react simu taneously.

5. The process of produc ng resins WhlCh comprises causing simultaneously a reaction comprises causing simultaneously a reaction between a phenolic body, acetone-and a formaldehyde body.

7. The process of producing resins which comprises causing simultaneously a reaction between a,

henoIic body, acetone oil and para-forma' dehyde.

CHARLES O. TERWILLIGER. 

